Process for the Production of Chlorinated Propanes Verfahren Zur Herstellung Von Chlorierten Propanen Procédé De Production De Propanes Chlorés - DocsLib

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(11) EP 2 785 671 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 17/10 (2006.01) C07C 19/01 (2006.01) 01.03.2017 Bulletin 2017/09 (86) International application number: (21) Application number: 12799450.7 PCT/US2012/067268

(22) Date of filing: 30.11.2012 (87) International publication number: WO 2013/082410 (06.06.2013 Gazette 2013/23)

(54) PROCESS FOR THE PRODUCTION OF CHLORINATED PROPANES VERFAHREN ZUR HERSTELLUNG VON CHLORIERTEN PROPANEN PROCÉDÉ DE PRODUCTION DE PROPANES CHLORÉS

(84) Designated Contracting States: (74) Representative: Bumke, Jakob Wenzel et al AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Greaves Brewster LLP GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Copa House PL PT RO RS SE SI SK SM TR Station Road Cheddar BS27 3AH (GB) (30) Priority: 02.12.2011 US 201161566213 P (56) References cited: (43) Date of publication of application: EP-A1- 0 164 798 WO-A1-01/38271 08.10.2014 Bulletin 2014/41 WO-A1-2009/015304 WO-A1-2009/085862 WO-A1-2012/166393 US-A- 6 118 018 (73) Proprietor: Blue Cube IP LLC US-A1- 2009 270 568 US-B1- 6 825 383 Midland MI 48674 (US) • LEWIS F. HATCH ET AL: JOURNAL OF THE (72) Inventors: AMERICAN CHEMICAL SOCIETY, vol. 74, no. 13, • GRANDBOIS, Matthew Lee 5 July 1952 (1952-07-05), pages 3328-3330, Midland, Michigan 48640 (US) XP55050199, ISSN: 0002-7863, DOI: • CHEN, Xiaoyun 10.1021/ja01133a033 Midland, Michigan 48642 (US) • KRUPER, William J. Jr. Sanford, Michigan 48657 (US)

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 785 671 B1

Printed by Jouve, 75001 PARIS (FR) 1 EP 2 785 671 B1 2

Description 1,1,1,3-tetrachloropropane and chlorine, for the manufacture of 1,1,2,3-tetrachloropropene from 1,1,1,2,3- [0001] The present invention relates to processes for pentachloropropane, for the manufacture of 1,1,2,3-tet- the production of chlorinated propanes in a nonaqueous rachloropropene from 1,1,1,3-tetrachloropropane and media. 5 chlorine, and for the manufacture of 1,1,2,3-tetrachloropropene from carbon tetrachloride, ethylene, and chlo- BACKGROUND rine. [0008] US 6825383 B1 describes a process for re- [0002] Hydrofluorocarbon (HFC) products are widely giospecific chlorination of an aromatic or aliphatic com- utilized in many applications, including refrigeration, air 10 pound with a chlorine source comprising a metal chloride conditioning, foam expansion, and as propellants for aer- other than Cl2 or SO2Cl2 in presence of hypervalent io- osol products including medical aerosol devices. Al- dine catalyst and in acidic medium. though HFC’s have proven to be more climate friendly than the chlorofluorocarbon and hydrochlorofluorocar- BRIEF DESCRIPTION bon products that they replaced, it has now been discov- 15 ered that they exhibit an appreciable global warming po- [0009] The present invention provides efficient proc- tential (GWP). esses for the production of highly chlorinated propanes. [0003] The search for more acceptable alternatives to More particularly, the processes make use of one or more current fluorocarbon products has led to the emergence inorganic iodine salts as part of a mixed catalyst system of hydrofluoro-olefin (HFO) products. Relative to their 20 further comprising at least one Lewis acid selected from predecessors, HFOs are expected to exert less impact the group consisting of ferric chloride, antimony pentaflu- on the atmosphere in the form of a lesser, or no, detri- oride, boron trichloride, aluminum trichloride, stannic mental impact on the ozone layer and their lower GWP chloride or combinations of these. The use of inorganic as compared to HFC’s. Advantageously, HFO’s also ex- iodine salts is advantageous as compared to convention- hibit low flammability and low toxicity. 25 al processes, in that inorganic iodine salts are not as [0004] As the environmental, and thus, economic im- corrosive or volatile as elemental iodine when employed portance of HFO’s has developed, so has the demand at conventional levels, and so, are more readily and con- for precursors utilized in their production. Many desirable veniently incorporated into large scale manufacturing HFO compounds, e.g., such as 2,3,3,3-tetrafluoroprop- process. Because the present processes are conducted 1-ene or 1,3,3,3- tetrafluoroprop-1-ene, may typically be 30 in a nonaqueous media, the inorganic iodine salts are produced utilizing feedstocks of chlorocarbons, and in recoverable and/or reusable, providing significant cost particular, highly chlorinated alkanes, e.g., tetra- and savings to the process. Further cost savings are provided pentachloroalkanes. in that low intensity process conditions, e.g., low temper- [0005] Unfortunately, these higher chlorides have atures, ambient pressure and minimal reactor residence proven difficult to manufacture using acceptable process 35 time, are utilized. conditions and in commercially acceptable regioselectiv- [0010] In one aspect, the present invention provides a ities and yields. For example, conventional processes for process for the production of chlorinated propanes. The the production of pentachloropropanes provide unac- process comprises catalyzing the chlorination of a feed- ceptable selectivity to the desired pentachloropropane stream comprising one or more propanes in a nonaque- isomer(s), i.e., 1,1,2,2,3-pentachloropropane, make use 40 ous media with a mixed catalyst system comprising one of suboptimal chlorinating agents, require the use of high or more inorganic iodine salts, optionally less than 10,000 intensity process conditions and/or catalyst systems that ppm elemental iodine, and at least one Lewis acid se- are difficult to utilize in large scale production processes lected from the group consisting of ferric chloride, anti- and/or are wholly or partly unrecoverable or otherwise mony pentafluoride, boron trichloride, aluminum trichlo- unreusable. 45 ride, stannic chloride or combinations of these. Although [0006] It would thus be desirable to provide improved an inorganic iodine salt is used as part of the catalyst processes for the production of chlorocarbon precursors system, and in some advantageous embodiments, no useful as feedstocks in the synthesis of refrigerants and iodine is added to the starting propane. In some embod- other commercial products. More particularly, such proc- iments, the one or more inorganic iodine salts may com- esses would provide an improvement over the current 50 prise hypoiodites (IO-), iodites (IO2-), iodates (IO3-), state of the art if they provided a higher regioselectivity and/or periodates (IO4-), including metaperiodates and relative to conventional methods, made use of optimal orthoperiodates, or combinations of these. In some em- chlorinating agents, required low intensity process con- bodiments, the concentration of elemental iodine used, ditions, made use of catalyst systems and/or initiators if any, may be from 1 ppm to 5000 ppm, or from 5 ppm more amenable to use in large-scale processes, such as 55 to 1000 ppm, or from 10 ppm to 100 ppm. The source of those that may be recovered or otherwise reused. chlorine atoms may comprise chlorine gas, sulfuryl chlo- [0007] WO 2009/085862 A1 describes methods for the ride or a combination of these, and in some embodiments manufacture of 1,1,1,2,3-pentachloropropane from comprises sulfuryl chloride, which may also act as a dilu-

2 3 EP 2 785 671 B1 4 ent or solvent as well as a chlorine source. The propane stream comprising one or more propanes with one or may initially be unchlorinated, or, may already comprise more inorganic iodine salt and at least one Lewis acid. chlorine atoms, and may comprise any number of carbon Further, the processes take place in a nonaqueous me- atoms. dia, and as a result, the one or more inorganic iodine 5 salts may be recovered in whole or in part, and/or reused. DETAILED DESCRIPTION The use of an inorganic iodine salt is further advantageous in that inorganic iodine salts do not present the [0011] The present specification provides certain def- volatility and corrosion issues that can be presented by initions and methods to better define the present inven- elemental iodine when used at conventional levels, as is tion and to guide those of ordinary skill in the art in the 10 used in conventional processes for the production of practice of the present invention. Provision, or lack of the chlorinated alkanes. provision, of a definition for a particular term or phrase [0017] Any inorganic iodine salt can be used in the is not meant to imply any particular importance, or lack mixed catalyst system, and those of ordinary skill in the thereof. Rather, and unless otherwise noted, terms are art are expected to be familiar with many. Suitable ex- to be understood according to conventional usage by 15 amples include, but are not limited to, hypoiodites (IO -), those of ordinary skill in the relevant art. iodites (IO2-), iodates (IO3-), and/or periodates (IO 4-), in- [0012] The terms "first", "second", as used herein do cluding mesoperiodates and orthoperiodates, or combi- not denote any order, quantity, or importance, but rather nations of these. Specific examples of inorganic iodine are used to distinguish one element from another. Also, salts include, but are not limited to sodium iodate, silver the terms "a" and "an" do not denote a limitation of quan- 20 iodate, calcium iodate, potassium iodate, iodic acid, so- tity, but rather denote the presence of at least one of the dium periodate, potassium periodate, barium periodate, referenced item, and the terms "front", "back", "bottom", and periodic acid, and derivatives or combinations of any and/or "top", unless otherwise noted, are merely used for number of these. convenience of description, and are not limited to any [0018] In other embodiments, elemental iodine may one position or spatial orientation. 25 additionally be used, but at levels much lower than pre- [0013] If ranges are disclosed, the endpoints of all viously thought to be effective. That is, it has now been ranges directed to the same component or property are discovered that amounts of iodine much lower than con- inclusive and independently combinable (e.g., ranges of ventionally utilized, e.g., 0.01 wt%, provide improve- "up to 25 wt.%, or, more specifically, 5 wt.% to 20 wt.%," ments in yield and selectivity while yet not presenting the is inclusive of the endpoints and all intermediate values 30 corrosion and volatility issues that may arise when these of the ranges of "5 wt.% to 25 wt.%," etc.). As used herein, conventional levels are utilized. More specifically, percent (%) conversion is meant to indicate change in amounts of elemental iodine of from 1 ppm to 5000 ppm, molar or mass flow of reactant in a reactor in ratio to the or from 5 ppm to 1000 ppm, or from 10 ppm to 100 ppm, incoming flow, while percent (%) selectivity means the have now surprisingly been discovered to provide selec- change in molar flow rate of product in a reactor in ratio 35 tivities to the desired chloropropanes of greater than to the change of molar flow rate of a reactant. 60%,in some casesgreater than 70%, and insome cases [0014] Reference throughout the specification to "one greater than 80%. This is a significant improvement over embodiment" or "anembodiment" means that a particular processes wherein no iodine is used at all, wherein con- feature, structure, or characteristic described in connec- versions of e.g., less than 60% can be seen. Since ele- tion with an embodiment is included in at least one em- 40 mental iodine can be costly, significant cost savings are bodiment. Thus, the appearance of the phrases "in one also provided by using the smaller amounts described embodiment" or "in an embodiment" in various places herein. Combinations of one or more inorganic iodine throughout the specification is not necessarily referring salts and elemental iodine may be used. to the same embodiment. Further, the particular features, [0019] The mixed catalyst system used in the process structures or characteristics may be combined in any suit- 45 also comprises at least one Lewis acid selected from the able manner in one or more embodiments. group consisting of ferric chloride, antimony pentafluo- [0015] As used herein, the term "inorganic iodine salt" ride, boron trichloride, aluminum trichloride, stannic chlo- is meant to include any inorganic salt, incorporating, or ride and combinations of two or more of these. In some otherwise capable of providing or forming in a reaction embodiments, anhydrous aluminum chloride may desir- mixture, at least one hypervalent iodine species. Typi- 50 ably be utilized as the at least one Lewis acid. cally, such compounds may further be characterized in [0020] Generally speaking, enough of the mixed cata- that they comprise at least metal and iodine elements. lyst system should be utilized to provide some improve- The term "hypervalent", in turn, refers to iodine sources ment to reaction process conditions (e.g., a reduction in having oxidation states of greater than or equal to +1, required temperature) and desirably, reaction selectivity, e.g., +1, +3, +5, +7, etc. 55 but yet not be more than will provide any additional ben- [0016] The present invention provides efficient proc- efit, if only for reasons of economic practicality. For pur- esses for the production of chlorinated propanes. The poses of illustration only, then, it is expected that useful present processes catalyze the chlorination of a feed- concentrations of the inorganic iodine salt, in a batch

3 5 EP 2 785 671 B1 6 process, will range from 0.01% to 30% by weight with multitube exchanger followed by vapor liquid disengage- respect to the alkane and/or alkene, or from 0.1% to 20%, ment tank or vessel can also be used. or from 1% to 10 wt%, inclusive of all subranges there- [0024] The present process makes use of one or more between. Surprisingly low levels of elemental iodine are propanes to produce the desired chlorinated propanes. effective, e.g., from 1 ppm to 5000 ppm, or from 5 ppm 5 Propanes that are desirably chlorinated in a nonaqueous to 1000 ppm, or from 10 ppm to 100 ppm. Suitable media may benefit from application of the present proc- amounts of the Lewis acid will range from 0.01% to 20% ess. by weight each with respect to the dichlorinated alkane, [0025] Similarly, the propane may be unchlorinated, or or from 0.1% to 10%, or from 1% to 5 wt%, inclusive of may comprise chlorine atoms prior to application of the all subranges therebetween. For continuous processes, 10 process. That is, the propane may comprise any number it is possible that much lower concentrations, e.g., as of chlorine atoms, including zero. To some degree, the much as 5, or 10, or 15 or even 20 times lower will not number of chlorine atoms in the propane will be limited only be effective, but be effective over the entire course by the number of carbon atoms, as well as the chlorinated of plant operability. propane desirably produced. In some embodiments, the [0021] The chlorine atoms are desirably supplied by 15 propane may comprise from 0-4 chlorine atoms, or may chlorine gas, sulfuryl chloride, or both. Sulfuryl chloride comprise 1-3 chlorine atoms. In some embodiments, the

(SO2Cl2), can also act as a solvent for the mixed catalyst propane may be a mono-, di-, or trichlorinated propane, systems and/or reactions, thereby assisting in the provi- such as 1- or 2-chloropropane, 1,2-dichlorinated pro- sion of an acceptable reaction rate and/or yield. And so, pane, and/or 1,1,2-trichlorinated propane. in some embodiments, sulfuryl chloride may desirably be 20 [0026] In one exemplary process, a dichloropropane, used as the chlorinating agent. e.g., 1,2-dichloropropane, is utilized as a starting material [0022] In some embodiments, including those wherein and reacted with sulfuryl chloride in the presence of so- chlorine is used as a chlorinating agent rather than sul- dium iodate at a temperature of from 55°C to 75°C, am- furyl chloride, a solvent may be used in the present proc- bient pressure and a reactor occupancy of less than five esses. Desirably, any solvent will be inert to the desired 25 hours to produce a pentachloropropane, e.g., 1,1,2,2,3- chemistry, allow for adequate mass transfer during the pentachloropropane at regioselectivities of greater than chemical reaction, and create a homogenous phase to 10:1, or greater than 20:1 or greater than 30:1, or even insure uniform reactivity throughout the reactor. Chloro- greater than 40:1, over other pentachloropropane prod- carbon solvents are especially well suited for the present ucts. processes due to their ease in handling and relative re- 30 [0027] Some embodiments of the invention will now be sistance to the desired chemistry, and many of these are described in detail in the following examples. known to those of ordinary skill in the art. For example, [0028] Example 1. Chlorination of 1,2-dichloropropane suitablechlorocarbon solvents include,but are not limited to 1,1,2,2,3-pentachloropropane using sodium periodate to carbon tetrachloride, methylene chloride, chloroform, as inorganic iodine salt, aluminum chloride as Lewis acid 1,2,3-trichloropropane, 1,1,2,3-tetrachloropropane, and 35 and sulfuryl chloride as chlorinating agent. 1,1,2,2,3,3-hexachloropropane. In some embodiments, [0029] 17g sulfuryl chloride and 2.5g aluminum chlo- the chlorocarbon solvent may comprise methylene chloride is charged to a reactor equipped with a magnetic stir ride or 1,2,3-trichloropropane. bar and reflux condenser. The reaction mixture is heated [0023] The reaction conditions under which the proc- to 60°C and then 4.1g of 1,2-dichloropropane is charged. ess is carried out are advantageously low intensity. That 40 The reaction is allowed to stir for 35 minutes, where GC is, low temperatures, e.g., of less than 100°C, or less analysis indicated that >99% of the 1,2-dichloropropane than 90°C, or less than 80°C or less than 70°C, or less had been reacted to form primarily 1,1,2-trichloropro- than 60°C, may be utilized and the desired selectivities pane. to the desired chlorinated alkanes yet be realized. In [0030] An additional 15g of sulfuryl chloride along with some embodiments, temperatures of from 40°C to 90°C, 45 1g of sodium periodate is added. The reaction is allowed or from 50°C to 80°C, or from 55°C to 75°C may be uti- to react for a total 4 hours before being cooled back to lized. Similarly, ambient pressure is suitable for carrying ambient temperature. The crude reaction mixture is fil- out the process, or pressures within 250, or 200, or 150, tered to collect the sodium periodate catalyst as a wet or 100, or 50, or 40, or 30, or 20, or even 10 psi (1724, cake that is washed with methylene chloride to give 0.8g or 1379, or 1034, or 689, or 345, or 276, or 207, or 138, 50 of recovered sodium periodate. or even 69 kPa) of ambient are suitable. Reactor occu- [0031] The reaction mixture and methylene chloride pancy may also be minimized with the desired selectiv- wash are combined, slowly poured into an ice water bath, ities yet seen - for example, reactor occupancy times of and allowed to stir until quenched. The organic and aque- less than 20 hours, or less than 15 hours, or less than ous phases are separated and the aqueous phase is ex- 10 hours, or less than 9, 8, 7, 6, or even 5 hours, are55 tracted with an equal volume of methylene chloride. The possible. The reactor may be any suitable liquid phase combined organic fractions are dried over magnesium reactor, such as a batch or continuous stirred tank auto- sulfate, the excess solvent is removed by rotary evapo- clave reactor with an internal cooling coil. A shell and rator, and the final product is isolated as a colored oil.

4 7 EP 2 785 671 B1 8

[0032] GC and NMR analysis of the final product mix- are dried over magnesium sulfate, the excess solvent is ture shows a yield of 4.7g of 1,1,2,2,3-pentachloropro- removed by rotary evaporator, and the final product was pane, 0.7g of tetrachloropropane isomers, 0.4g of 1,1,2- isolated as a colored oil. trichloropropane, 0.3g of hexachloropropane isomers, [0041] GC and NMR analysis of the final product mix- and 0.2g of 1,2,3-trichloropropane. 5 ture shows a yield of 5.4g of 1,1,2,2,3-pentachloropro- [0033] Example 2. Chlorination of 1,2-dichloropropane pane, 0.6g of tetrachloropropane isomers, 0.4g of hex- to 1,1,2,2,3-pentachloropropane using recovered sodi- achloropropane isomers, 0.3g of 1,1,2-trichloropropane um periodate as inorganic iodine salt, aluminum chloride and 0.2g of 1,2,3-trichloropropane. as Lewis acid and sulfuryl chloride as chlorinating agent. [0042] Example 4. Chlorination of 1,2-dichloropropane [0034] 9.3g sulfuryl chloride and 1.3g aluminum chlo- 10 to 1,1,2,2,3-pentachloropropane using sodium iodate as ride is charged to a reactor equipped with a magnetic stir inorganic iodine salt, aluminum chloride as Lewis acid bar and reflux condenser. The reaction mixture is heated and sulfuryl chloride as chlorinating agent. to 60°C and charged with 2.3g of 1,2-dichloropropane. [0043] 17g sulfuryl chloride, 0.6g aluminum chloride, The reaction is allowed to stir for 35 minutes, when GC and 0.8g of sodium iodate is charged to a reactor analysis indicates that >99% of the 1,2-dichloropropane 15 equipped with a magnetic stir bar and reflux condenser. has reacted to form primarily 1,1,2-trichloropropane. The reaction mixture is heated to 60°C and then 4.1g of [0035] An additional 7.9g of sulfuryl chloride along with 1,2-dichloropropane is added. The reaction is allowed to 0.5g of sodium periodate recovered from Example 1 is stir for a total 4 hours before being cooled back to ambient charged. The reaction is allowed to react for a total 4 temperature. hours before being cooled back to ambient temperature. 20 [0044] The reaction mixture is slowly poured into an The crude reaction mixture is filtered to collect the sodium ice water bath and allowed to stir until quenched. The periodate catalyst as a wet cake that is washed with meth- organic and aqueous phases are separated and the ylene chloride to give 0.45g of recovered sodium perio- aqueous phase is extracted with an equal volume of date. methylene chloride. The sodium iodate is recovered in [0036] The reaction mixture and methylene chloride 25 the aqueous wash as indicated by ion chromatography wash are combined, slowly poured into an ice water bath, analysis. The combined organic fractions are dried over and allowed to stir until quenched. The organic and aque- magnesium sulfate, the excess solvent is removed by ous phases are separated and the aqueous phase is ex- rotary evaporator, and the final product is isolated as a tracted with an equal volume of methylene chloride. The colored oil. combined organic fractions are dried over magnesium 30 [0045] GC and NMR analysis of the final product mix- sulfate, the excess solvent is removed by rotary evapo- ture shows a yield of 2.3g of 1,1,2,2,3-pentachloropro- rator, and the final product is isolated as a colored oil. pane, 1.4g of 1,1,2-trichloropropane, 0.9g of tetrachloro- [0037] GC and NMR analysis of the final product mix- propane isomers, 0.8g of 1,2,3-trichloropropane, and ture shows a yield of 3.1g of 1,1,2,2,3-pentachloropro- 0.2g of hexachloropropane isomers. pane, 0.5g of hexachloropropane isomers, 0.1g of 1,2,3- 35 [0046] Example 5 (not according to the invention). trichloropropane, and 0.1g of tetrachloropropane iso- Chlorination of 1,1,2-trichloropropane to 1,1,2,2,3-pen- mers. tachloropropaneusing low levels ofelemental iodine, alu- [0038] Example 3. Chlorination of 1,2-dichloropropane minum chloride as Lewis acid, chlorine as chlorinating to 1,1,2,2,3-pentachloropropane using sodium iodate as agent, and methylene chloride as chlorocarbon solvent. inorganic iodine salt, aluminum chloride as Lewis acid 40 [0047] A product stream is prepared by feeding chlo- and sulfuryl chloride as chlorinating agent. rine gas at 30 sccm through a starting mixture of 22.6wt% [0039] 17g sulfuryl chloride and 2.5g aluminum chlo- 1,2-dichloropropane, 1.3wt% aluminum chloride, and ride is charged to a reactor equipped with a magnetic stir 76.1wt% methylene chloride at 130psig and 70°C until bar and reflux condenser. The reaction mixture is heated GC analysis indicates that the starting dichloropropane to 60°C and then 4.1g of 1,2-dichloropropane is charged. 45 has undergone 68% conversion to give 1,1,2-trichloro- The reaction is allowed to stir for 35 minutes, when GC propane as the major intermediate species. This stream analysis indicates that >99% of the 1,2-dichloropropane is charged with 35ppm elemental iodine dissolved in has reacted to form primarily 1,1,2-trichloropropane. 15mL of methylene chloride based on initial dichloropro- [0040] An additional 15g of sulfuryl chloride along with pane within the reaction mixture. The resulting mixture 0.5g of sodium iodate is charged. The reaction is allowed 50 is allowed to stir until 36.1% conversion of the 1,1,2- to react for a total 4 hours before being cooled back to trichloropropane intermediate is observed to give the de- ambient temperature. The reaction mixture is slowly sired pentachloropropane and its precursors in 82.3% poured into an ice water bath and allowed to stir until selectivity over the undesired byproducts of 1,1,2,2,3,3- quenched. The organic and aqueous phases are sepa- hexachloropropane and 1,1,2,3-tetrachloropropane. rated and the aqueous phase is extracted with an equal 55 When viewed in light of Example 6, this example shows volume of methylene chloride. The sodium iodate is re- that virtually the same conversion of 1,1,2-trichloropro- covered in the aqueous wash as indicated by ion chro- pane with virtually the same selectivity to the desired pen- matography analysis. The combined organic fractions tachloropropane when a significantly lower amount of el-

5 9 EP 2 785 671 B1 10 emental iodine is used than is conventional. When or combinations of these, and one or more inorganic viewed in combination with Example 7, this example iodine salts. shows that even these low levels of iodine result in significantly greater selectivities to the desired pentachlo- 2. The process of claim 1, wherein the source of chloropropanes than no elemental iodine at all. 5 rine atoms comprises chlorine gas, sulfuryl chloride [0048] Example 6 (not according to the invention). or a combination of these. Chlorination of 1,1,2-trichloropropane to 1,1,2,2,3-pentachloropropane using conventional levels of iodine, alu- 3. The process of claim 1, wherein the Lewis acid com- minum chloride as Lewis acid, chlorine as chlorinating prises aluminum chloride. agent, and methylene chloride as inert chlorocarbon sol- 10 vent. 4. The process of claim 1, wherein the process is con- [0049] A product stream is prepared by feeding chlo- ducted in the presence of a chlorocarbon solvent. rine gas at 30 sccm through a starting mixture of 22.6wt% 1,2-dichloropropane, 1.3wt% aluminum chloride, and 5. The process of claim 1, wherein the propane com- 76.1wt% methylene chloride at 130psig and 70°C until 15 prises from 0-4 chlorine atoms. GC analysis indicates that the starting dichloropropane has undergone 69.7wt% conversion to give 1,1,2-trichlo- 6. The process of claim 5, wherein the propane is a ropropane as the major intermediate species. This trichloropropane. stream is charged with 0.57wt% elemental iodine dissolved in 15mL of methylene chloride based on initial 20 7. The process of claim 1, 4 or 5, wherein the chlorin- dichloropropane within the reaction mixture. The result- ated propane comprises from 2-6 chlorine atoms. ing mixture is allowed to stir until 33.0% conversion of the 1,1,2-trichloropropane intermediate is observed to 8. The process of claim 7, wherein the chlorinated pro- give the desired pentachloropropane and its precursors pane comprises a pentachloropropane. in 85.4% selectivity over the undesired byproducts of 25 1,1,2,2,3,3-hexachloropropane and 1,1,2,3-tetrachloro- 9. The process of claim 8, wherein the chlorinated pro- propane. pane comprises 1,1,2,2,3-pentachloropropane. [0050] Example 7 (not according to the invention). Chlorination of 1,1,2-trichloropropane to 1,1,2,2,3-pen- 10. The process of claim 1, wherein the inorganic iodine tachloropropane in the absence of elemental iodine using 30 salt is recovered from the process. aluminum chloride as Lewis acid, chlorine as chlorinating agent, and methylene chloride as inert chlorocarbon sol- 11. The process of claim 1, wherein the inorganic iodine vent. salt comprises one or more hypoiodites, iodites, io- [0051] A product stream is prepared by feeding chlo- dates, periodates, or combinations of these. rine gas at 30 sccm through a starting mixture of 22.6wt% 35 1,2-dichloropropane, 1.3wt% aluminum chloride, and 12. Theprocess ofclaim 11, whereinthe inorganiciodine 76.1wt% methylene chloride at 130psig and 70°C until salt comprises sodium iodate, silver iodate, calcium GC analysis indicates that the starting dichloropropane iodate, potassium iodate, iodic acid, sodium perio- has undergone 71.5wt% conversion to give 1,1,2-trichlo- date, potassium periodate, barium periodate, peri- ropropane as the major intermediate species. This40 odic acid, or derivatives or combinations of any stream is charged with 15mL of methylene chloride. The number of these. resulting mixture is allowed to stir until 28.3% conversion of the 1,1,2-trichloropropane intermediate is observed to 13. Theprocess ofclaim 12, whereinthe inorganiciodine give the desired pentachloropropane and its precursors salt comprises sodium iodate, potassium iodiate, so- in 53.9% selectivity over the undesired byproducts of 45 dium periodate, or combinations of these. 1,1,2,2,3,3-hexachloropropane and 1,1,2,3-tetrachloropropane. Patentansprüche

Claims 50 1. Verfahren zur Herstellung chlorierter Propane, um- fassend, in einem nichtwässrigen Medium, das Ka- 1. A process for the production of chlorinated propanes talysieren der Chlorierung eines Zufuhrstroms, der comprising, in a nonaqueous media, catalyzing the ein oder mehrere Propane umfasst, mit einem ge- chlorination of a feedstream comprising one or more mischten Katalysatorsystem, das zumindest eine propanes with a mixed catalyst system comprising 55 Lewis-Säure, ausgewählt aus der Gruppe, beste- at least one Lewis acid selected from the group con- hend aus Eisen(III)-chlorid, Antimonpentafluorid, sisting of ferric chloride, antimony pentafluoride, bo- Bortrichlorid, Aluminiumtrichlorid, Zinnchlorid oder ron trichloride, aluminum trichloride, stannic chloride Kombinationen davon, und ein oder mehrere anor-

6 11 EP 2 785 671 B1 12

ganische Iodsalze umfasst. trichlorure d’aluminium, du chlorure stanneux ou de combinaisons de ceux-ci, et un ou plusieurs sels d’io- 2. Verfahren nach Anspruch 1, wobei die Quelle von de inorganiques. Chloratomen Chlorgas, Sulfurylchlorid oder eine Kombination davon umfasst. 5 2. Procédé selon la revendication 1, dans lequel la source d’atomes de chlore comprend du chlore ga- 3. Verfahren nach Anspruch 1, wobei die Lewis-Säure zeux, du chlorure de sulfuryle ou une combinaison Aluminiumchlorid umfasst. de ceux-ci.

4. Verfahren nach Anspruch 1, wobei das Verfahren in 10 3. Procédé selon la revendication 1, dans lequel l’acide Anwesenheit eines Chlorkohlenwasserstoff-Sol- de Lewis comprend du chlorure d’aluminium. vens durchgeführt wird. 4. Procédé selon la revendication 1, dans lequel le pro- 5. Verfahren nach Anspruch 1, wobei das Propan 0 bis cédé est réalisé en présence d’un solvant chlorocar- 4 Chloratome umfasst. 15 bure.

6. Verfahren nach Anspruch 1, wobei das Propan ein 5. Procédé selon la revendication 1, dans lequel le Trichlorpropan ist. propane comprend de 0 à 4 atomes de chlore.

7. Verfahren nach Anspruch 1, 4 oder 5, wobei das20 6. Procédé selon la revendication 5, dans lequel le chlorierte Propan 2 bis 6 Chloratome umfasst. propane est un trichloropropane.

8. Verfahren nach Anspruch 7, wobei das chlorierte 7. Procédé selon la revendication 1, 4 ou 5, dans lequel Propan ein Pentachlorpropan umfasst. le propane chloré comprend de 2 à 6 atomes de chlo- 25 re. 9. Verfahren nach Anspruch 8, wobei das chlorierte Propan 1,1,2,2,3-Pentachlorpropan umfasst. 8. Procédé selon la revendication 7, dans lequel le propane chloré comprend un pentachloropropane. 10. Verfahren nach Anspruch 1, wobei das anorgani- sche Iodsalz von dem Verfahren zurückgewonnen 30 9. Procédé selon la revendication 8, dans lequel le wird. propane chloré comprend du 1,1,2,2,3-pentachloropropane. 11. Verfahren nach Anspruch 1, wobei das anorgani- sche Iodsalz ein oder mehrere Hypoiodite, Iodite, 10. Procédé selon la revendication 1, dans lequel le sel Iodate, Periodate oder Kombinationen davon um- 35 d’iode inorganique est récupéré à partir du procédé. fasst. 11. Procédé selon la revendication 1, dans lequel le sel 12. Verfahren nach Anspruch 11, wobei das anorgani- d’iode inorganique comprend un ou plusieurs hy- sche Iodsalz Natriumiodat, Silberiodat, Calciumio- poiodites, iodites, iodates, periodates ou des com- dat, Kaliumiodat, Iodsäure, Natriumperiodat, Kali- 40 binaisons de ceux-ci. umperiodat, Bariumperiodat, Periodsäure oder De- rivate oder Kombinationen einer beliebigen Anzahl 12. Procédé selon la revendication 11, dans lequel le davon umfasst. sel d’iode inorganique comprend l’iodate de sodium, l’iodate d’argent, l’iodate de calcium, l’iodate de po- 13. Verfahren nach Anspruch 12, wobei das anorgani- 45 tassium, l’acide iodique, le periodate de sodium, le sche Iodsalz Natriumiodat, Kaliumiodat, Natriumpe- periodate de potassium, le periodate de baryum, riodat oder Kombinationen davon umfasst. l’acide periodique ou des dérivés ou combinaisons de tout nombre de ceux-ci.

Revendications 50 13. Procédé selon la revendication 12, dans lequel le sel d’iode inorganique comprend l’iodate de sodium, 1. Procédé de production de propanes chlorés com- l’iodate de potassium, le periodate de sodium ou des prenant, dans un milieu non aqueux, la catalyse de combinaisons de ceux-ci. la chloration d’un courant comprenant un ou plusieurs propanes avec un système de catalyseur mix- 55 te comprenant au moins un acide de Lewis choisi dans le groupe constitué du chlorure ferrique, du pentafluorure d’antimoine, du trichlorure de bore, du

7 EP 2 785 671 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• WO 2009085862 A1 [0007] • US 6825383 B1 [0008]

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